Cellulose thiourethane esters and ethers and process for making same



. horn, ebonite,: ivory,

.. 55 ficial'material asused V Patented June 19,

' um-Tao "sTATEi -s OFFICE.-

mon LILIENFELD, or vmmim'ausrara.

cnuuaosn 'rmouanrnans ns'rnas annn'rnnas um raocnss son MAKING slum.

Io Drawing. Application fled s eater; 1925,

By the present invention new c lu-- lose compounds are produced by ca sing I an ester of an inor anic acid to react with a saltof an N-substituted or not substituted 6 thiourethane. v(thiocarbamic acid esters or i xanthic amides) of cellulose, or with an N'- substituted or not substituted thiourethane of cellulose, in presence of a' basic substance, particularly an alkali, 1 The products have different properties in a; accordance with the working conditions, particularly with the nature andthe proportion of. the inorganic acid ester used. In'i-llus- -'-tration I, give here the properties of some categories of the new cellulose compounds which show particularly mai'ked difierences in their properties, especially their behaviourto solvents. To the first category belong' .-compounds which dissolve only in basic solvents, like aqueous alkalies, aqueous .pyridine solutions and aqueous solutions of organic amines. To the second category belong compounds which dissolve in aqueous.

- tives can be worked up, either by drying, or

precipitation or coagulation with" the aid'of a suitable precipitant, into valuable technical roducts, for example plastic masses of all kinds, such assubstitutes for celluloid, 7 glass, tortoise shell, wood and the like yarmshes, lacquers, layers of all kinds; skins (including photographic films); artificial fibres and threads, particularly artificial silk; adhesives and cements;

. finishes and coatings of all kinds on'textile threads and fabrics, paper, leather and the I like; vwater-proof materialsjsubst'itutes for wax-cloth andoil-cloth; artificial leather; bed sheets; bookbinders cloth, tracing cloth; electrical insulation masses a'nd the like.

- 1 Ihe expression artificial materials. used in the specification eludes all the artificial materials mentioned in the preceding para aph.v The term arti- 1n the following claims made for example as described in patent .ap-

an N substituted thiourethane which is solumixin'g apparatus, such as a mill, .mach ne,

and in the claims in Serial No. 57,018, and in Austria Qctohe r 11, 1824.1

used in the further sense that it is intended 7 thereby to exclude the-esters of the thiourethanes as chemical compounds per" se but. is designed to include matter made from or including the esters. 7

In themanu'facture of these new cellulose. compounds-the working conditions may be a varied within wide limits. For this reason the invention. so far.as it concerns its essential feature is not to be confined to the details of the following exposition or the examples which illustrate it. I One mode of carrying out the manufacture consists in converting, for example, an N- substituted thiourethane of cellulose or of a conversion product or derivative of cellulose -(made for example by the process described in patent application Ser. No. 727,805) or a not.substituted thiourethane (such as is.

plication Ser. No. 727,806) inflcruiie condi- 'tion,- or ina condition purified by any suitable method, into a salt (for example a silver salt,'by treating an ammoniacal solution of.

ble in ammonia, with' ammoniacal isilver nitrate. solutionor'an alkali metal salt or .the like) and treating this s with an alkyl-, aralkylor-aryl-ester of an inorganic acid, in the'cold or with aid of-heat,

If an alkali metal salt is to be used the thiourethane may for examplebe dissolved in alkali solution and the latterbrought together with the inorganic acid ester.

Or the thiourethane may be incor orated with the alkali in solid form (a vantageously pulverized), or with a strong'alkali solution (for example of 25-50 rper cent strength), or. with'a mixture of solid caustic alkali with saturated alkali solution, for instance the dry or moist thiourethane may be rubbed or kneaded together with. the solid alkali 'or the strong alkali solution or the mixture of solid caustic alkali with saturated alkali solution in an energeticalllyn acting eading reaker, edge runner, or the like. The alkali can be used; in the calculated proportion or in excess thereof (calculated on thethiourethane or on theester of the 1 Iinorganicacid oron both).

Inorganic acid. esters suitable for .the manufacture are halogen esters (halogenalkyls, halogen-aralkyls, halogen-aryls), sulphuriaacid esters, phosphoric acidesters or the like. Theester may be undiluted or diluted with suitable solvents benzene or the like). 1 k The final product of the reaction maybe isolated when the operation has been carried out in solution'by separating b filtration, straining, centrifuging or the li e fromthe '(such as benzol,

' mother liquor, washing with water and drying; or it may be dissolved and applied to technical purposes-either after previous separation of the bulk of the washing water by pressing, centrifuging orthe like, or afterprevious drying. T e precipitate may treated before or after washing with a dilute acid (for example sulphuric acid of 5-10 er cent strength) and then washed and drie If the operation is not conducted in solution the final product may be worked up by mixing the reaction mixture after the reaction is completed with cold or hot water, 001- lecting the undissolved final product on a suitable filtering apparatus, centrifuge or the like, and washing it with, cold or hot water.

The further working up may be conducted as described above.

From the mode of their formation the new Cellulose xanthanlllde The following mats illustrate the in vention theparts being by weight Example -l.-100 parts of a phenylor tolyl-thiourethane, made according. to Example 1 or 2 or 6 (in the latter case without neutralizing the viscose or reaction mixture at all) of patent application Ser. No.- 727,--

l -'805, are dissolved'in 4900 parts of a caustic soda solution of 10 per cent strength. The

- solution, filtered or strained if necessary, is mixed with 600-1000 parts of di-ethyl tion, crafter a longer time (1-8 days -filtration, centrifuging, decant'ation. or the solubility properties: It dissolves in alcohol sulphate and the Wholev stirred or shaken. After about half an houror an hour the final product of. the reaction is'precipitated."

It is separated from'the mother liquor immediately after there is no further precipitla y like, and washed with water until free from alkali. It is then stirred with sulphuric acid of 1-10 per cent strength, again filtered or centrifuged, washed freefrom sulphuric acid and dried, either' atreduced pressure or'in-the air.

After drying and comminution the prod- .uct is .a more. or less fine and sandy or flocculent powder, which has the following ,ondary react-ion alkyL, aral cellulose compounds should be esters of 'N-substituted or not substituted thiourethanes "of cellulose or esters of N-substituted imidothiolcarboxylic acids and. would be represented by a formula (in which a cellulosexanthanilide is taken as example) somewhat as follows:

wherein R is the-alkyl-, ,aralkylor arylradicalintroduced by the aforesaid reaction. I The results of analysis make it probable that in many cases asecondary reaction occurs besides the main reaction and in this seclor arylcoil-inc groups are substituted for the free hydroxylhydrogen atoms of the cellulosecomponent.

In all probability, the reaction between the salts of." the N-substituted cellulose thiourethanes and the inorganic esters takes place according to the following e nations in which, as an example, are taken" t e sodium salltaof a cellulose xanthanilide and ethyl- 1o 1 e:

O-(CuHn O) Ethyl/ester of cellulose xanthanlllde Phenylinndothiolcarboxyllc d esters! cellulose) I oxomlhowcm' alcohol mixture, glacial acetic acid, di-

ethylanilin'e-alcohol mixture, quinoline, a-dichlorhydrin, tetrachlorethane alcohol mixtlire, nitromethane-alcohol mixture acetylene-dichloride-alcohol mixture, pyridine, amyl-acetate-alcohol mixture, ethylene- .chlorhydrin, benz l-alcohol, mixtures of alcoholwith amy -acetate,. with 1' ethyl-benchloride, with ethyl-citrate, -with ethylnaphthol, with ethylen-bromide, with amylalcohol, with chloro-naphthalene, dibenzylzoate, with 'chlorobenzene, with *ethyleneether, allyl-alcohol, acetylene-acetone, eu-' genol, ethyl-lactate, a-picoline, epichlorhydrin,"ortho-chlorophenol and the like. 4 The solutions in volatile solvents, such as be'n zole-alcohol mixturer oimethyl-alcoholmethylacetate'mixture .or chloroform-aloe hol mixture or the like, may be worked up in admixture-with a. plasticizer such as camphor, phosphoric acid esters of phenols, for

' instance triphenylphosp'hate or tricresylphosphate and the like. to films or artificial threads, in short to all artificial materials,

' Calculated for: i

by evaporating the solvent or by precipitation by means of a suitable precipitant, such as water, salt solution or the like.

' Ultimate analysis 'giyes the following ures: '1 I offer: i Found:

O-(CuHuOmCnHs) O-(OflHuOaZCsH; cflm.u=c tHbN2C S-CgHg S.C:H5

C H NSO C H NSGm 0:53. 59 per cent. 55. per cent. 53. 93 per cent. H: 6. 4 per cent. 6. 81 per cent. 7 22 per cent. 'N= 2. 71 per cent. 2. 57 per cent. 35 per cent. S= 6.21 per cent. 5. 89 .per cent. '6. 23 per cent.

Assuming that the nitrogen. content is to be attributed to the presence of some impurities (which is improbable because even after redissolving the substance three or four times in benzene-alcohol mixture 1:1) and precipitating with ether, the body thus purilied still contains nearly the same proport1on of nitrogen), the foregoingl'figures would approximate a neutral thiolc'arbonic- 'acid-ethyl-ester of cellulose, in the cellulose comp'onent- (U complex) of which four or five h'ydroxyl-hydrogens' have been exchanged for ethyl-groups,"that is to say s.c,m 6 101115- 0.012111500AQ1H6 O- IaHnOmECIHA Emample fi -100 parts of a phenylor tolyl-thiourethane, made according to Example 1 or 2 or 6 (in the latter case with-' out neutralizing the viscose or reaction mix: ture at all) of patent application Ser. No. 727,805,.are dissolved in 4900 parts of a caustic sodasolution of 10 per cent strength.

[The solution, filtered or strained if necessary, is mixed with 300-400 parts of dition or the,like, and washed with water until free from alkali, and worked up in'the 'maniierdescribed in Example I. p

Thefinal product has properties and solu bility relationships which are more or "less the same as those of-the product obtained in accordance with Example I.

Ewample [IL- 100 parts of a phenyl-or tol-yl-thiourethahe, made accordingto Ex ample 1 or 2 pro (in theQlatter case without neutralizing the viscose or reaction mixture.

at all) ofapplication Ser. No. 727 ,805,-.are dissolved in 900 to .1900 parts -of a caustic Isoda solutionof 10 per cent strength. .The

solution, filtered or strained if necessary,

is mixed with 200-300 parts of di-ethyl sulphate and the whole continually kneadedi- After about half an hour or an hour the" final product of the reaction is precipitated. The neaction mixture is al owedto' stand at room-temperature for about 2 to reaction isseparated from themother liquor by filtration, centrifuging, decantation or the like, and washed with water until free from lkali.,' and worked up in-the manner 'described in Example I.

The final product has properties and solubility relationships whlch are more or less days and after this time the product of the' the same as those of, the product obtained in accordance with Exam le I.

Example [Va- -Mode. 0 operation as in the previous examples, with 'the difference that, from the beginning and until the precipitation vof the final pr'oduct takes place, the reaction mixture is cooled to 0" The coolin has the effect that even smaller quantities of di-ethyl sulphate suf-' fice to produce a' final product soluble in volatile solvents. q

V.100 parts of a phenylor ,tolyl-thiourethane', made according to Example 1 or 2 or 6 (in the latter case without neutralizing the viscose or reaction mixture at all) of patent application'Ser. No. 727 ,805,

' are dissolved in 4900 parts of a caustic soda solution of 1-3 percent stren h, The sola tion, filtered Y or strained i necessary, is

mixed with- 200-250 parts of di-ethyl sulf phate and the whole stirred or shaken.- After about half an'hour or n h0ur the final productof the reaction is p ecipitated. The

reaction mixture is then worked up in the manner described in Example 1.. .The final product of the reaction is soluble'in dilute alkali solution, for example caustic soda solution of 10 per cent strength, in aqueous alcohpland in acetic acid of 60-80. per cent 7 strength'.- Also,in aqueous pyridine and in aqueous solutions of organic bases. 7

- Ewamp'le VI. -'1 00 arts ofa phenyL: or -to1yl-thourethane, ma e in accordance with 'No. 727,805, are dissolved in 4900 parts 0t Example 1 or 2 of: patent application Ser.

caustic soda solution of "5-10 per cent" strength andth'e solution, filtered or strained .as may be necessary,- is heated on the water- 'bathto, 40-150 0. 600-1000 parts-of iii-ethyl ture-is'worked up as described in Example sulphate' are added and the whole isstirred or i-shaken. After some"minutes the final product of the reaction separates. The'mix- 1 1 L'either immediately or after it has been further heated for some hours at -5060-'C.

The final product resembles closely in its properties and solubilityrelationships that obtained as-described in Example I. a

in the foregoing examplesthere may be substituted for the caustic soda solution of 1-10 per cent strength, a stronger solution,

- ample di-methyl alkyl or halogen-aralkyl, such as ethylfor example one of the 20 per cent strength. It is also possible to-start with more con-. centrated thiourethane solutions, for example solutions of 20 per cent stren th in weaker or stronger caustic soda so utiou,

If more concentrated solutions of the N-substituted or not substituted thiourethanes in caustic soda solutions of, say, 10 to '20- per iodide, methyl, iodide, bromide, benzyl chloride or the like. ester selected has a low boiling point is desired to operate at a temperature above.

this boiling point, the operation would be conducted according to the boiling point,

- eithervin a reflux apparatus or in a closed vessel or pressure vessel, such as an autoclave. I

Example VII .100 arts of a phenyl-or tolyl-thiourethane, ma e as described in Example 1 or 2 of. patentapplication Ser. No.

727,805, are introduced into a cooled, energetically acting mixing apparatus, such as a kneadingmachine,

a breaker. or a mill, and 125 parts of powdered caustic soda are added in small portions. Thetemperatur of the mixture is maintainedv at 510 centigrade. -When the mass has become .unlform kneading or rubbing is interrupted.

. The final weight of the mass amounts .to

300-320 parts,

that is to say the mass has a sorbed -95 parts of water (obviously the operation may be suchthat a mixture of 125 parts of solid caustic 'sodawith 75-95 parts of water is introduced into the .inixing apparatus and the mixing conducted with ex-.

clusion of air).

The final product of-the mixing is intro;

duced into an autoclave eltherimmediately after the mixing or after it has been allowed to, rest for a longer or shorter period; the be movable or be provided tives, w; ich process comprises causing an viously cooled eth l-chl'oride are added, the

autoclave should with a stirring device; 200* parts. of preaut'o'clave is clo. and then heated in such a manner that the temperatureof themass attains 95-100 C. aiter 1-4 hours. At this temperature the mixture is kept with continuous movement'or stirring for 6-15 hours.

The cooled autoclave is opened and the mixture, if. necessary, broken up; it is then most thoroughly washed with cold ,or hotwater and. worked up in the manner describedin ExampleI.

The final product has properties and solubilityrelationships which are more or le$ the same as those of the product obtained in accordance withE'xample I.

Example II I .-.-The mode of operation re.-

sembles that described in Example VII, but

with the difi'erence that only -100-parts of caustic soda and correspondingly 125-160 parts of ethyl-chloride are used.

In all foregoing examples there may be substituted for the phenylor tolyl-thiourethane of cellulose another aryl-thiourethane, or an aralkyl-thiourethane, such as a benzyl-thiour'ethane' or an aliphatic thiourethane, such as monoor di-methylor ethyl-thiourethane, or'a not substituted thiourethane.

The expression iN-substituted or notsubstituted thiourethanes of cellulose in this specification and its claim means thiourethanes-or N-alkylor N-aralkylor N-arylthiourethanes of the cellulose group, of

which thecellulose component or components are either cellulose itself or a conver-.

sion product of cellulose, or a cellulose compound, for example those products ,which are btained when animoniao ,compou nds derlved from ammonia, in w ich at least one hydrogen atom of the ammonia has been exchanged for an a1cohol'radical','are allowed to acton a cellulose. xantho-fatty acid, that is to say products" which can be obtained by bringing together viscose and a mono-halogen fatty acid or a salt thereof.

In this specification and in the following clalms, the term an alcohol radi al-ris to be understood as including the s turated or unsaturated or anic complex which remains.

if the hgdroxyl group be taken away from a mono ydroxyllc alcohol or one or. more hydroxyl groups be taken awayi-froma dihydroxylic or polyhydroxylic alcohol. 1 -I claim: I

L'A process of making cellulose derivaester of an inorganic acid to act upon a salt of a thiourethane of the cellulose group.

2. A process of making cellulose derivatives, whichprocesscomprises causing an ester of an inorganic acid to act upon an alkali metal salt of 'a thiourethaii'e of the cellulosegroupi' 3. A rocess of making cellulose derivatives, which process comprises causing an demvae R 6. process of making cellulose derivatives, which process comprises. causing an esterof an inorganic acid to act upon an N-substitutd thiourethane of the cellulose ester of an inorganic acid to act upon a salt of. a phenyl-thiourethane of the cellulose group in pres'enceof an alkali.

7, A process of makingcellulose derivatives'wh-ich comprises causing an ester of an inorganic acid to actu onasolution of a .thiourethane of the ac lulose group in an alkali.' Y b '8. A process \of making cellulose derivatives which comprises'causing an ester of an inorganic acid to act upon a solution of an N-substituted thiourethane of the cellulose group an alkali.

9. A process "of making cellulose deriva- .tives, which process comprises causing an ester of an inorganic acid to act upona n thiourethane of the cellulose gnou in presen'ce of'water and an'alkali in suc manner that at least a part of the alkali is undissolved. J

10. A process of making cellulose deriva-' tives, which process comprises causing an .ester of an inorganic acidto act upon a salt of a thiourethane of thehc'ellulose group in .presence of water and an alkali in such,

manner that at least a undiss'olved. V v

11. A process of making cellulose der1va-' part of the alkali is lives, which process comprises causing anester of an inorganic acid to act upon "an ,.N-substi tuted thiourethane of the cellulose group in presence of water and an alkali in suchmannerthat at least a part of the alkali is undissolved.

12. A process of making cellulose derivatives,1'which process comprises, causing an.

i ester of an inorganic acid to act upon a salt of an N substitut'ed 'thiourethaneof the cellulose groupin presence of water and an alkali in such 'mann'er'that at least a part of. the alkali is undissolved. I

of an ,aryl-thiourethane of the cellulose group. ,a

- 13(A- process of makingcellulose derivatives, which process comprises causing an;

ester of an inorganic acid to act upon a salt 14. A process ofimaking cellulose'derivatives, which process comprises causing an .gr

ester'of ap inorganic-acid to act upon a solution of an aryLthicurethane of the L cellulose-group" in an alkali.

- 15: A process of 'king cellulose derira times, which process com rises causing an gr to act upon an ester of an inorganic aci aryl-thiourethane. of? the cellulose group in pre nce of water and an alkali in such man? ner that at least apart of the alkali is 'undissolved'.

16. A process ofjmakingcellulose deriva- -tives, which process comprises causingajn ester qtan inorganic acid to act upon a salt. thiourethanes at least" one Of an 'aIryl-thiourethane of the cellulose.

i such mannerthat at least apart of the is undissolved. 1

17. A process of making cellulose derivatives,"which process comprises causing an 18. A tives, which process comprises causing an ester of. an inorganic acidto act upon a solution of a phenyl-thiourethane of-thecellulose grpup in an alkali: I I 19. A process of makingcellulose derivatives, which PIOCGSS'COIIIPI'lSGS causing'an ester of an inorganic acid to act upon a phenyl-thiourethane of the cellulose group 1n presence of water and an alkali in such manner that at least a part oftlie alkali is I ourethanes' of the cellulose group.

anes of the cel ulose groupin which thiourethanes at least one hydrogen om of the v cal.

ourethanes at least one h droge n atom of the amide group is replacby an aryl group.

26. As new products, esters of thiourethanes ofthe cellulose group in which thisrethanes at least one hydrogen atom of the.

amide group is replaced I) a phenyl group.

27. As new products, a 1 esters of thiourethanes of the cellulose group in which thiourethanes at least one hydrogen atom of y? an aryl the amido group is replaced DUI). I f I 28. As new products, ethylesters of thiourethanes of'the cellulose group-in which 23." As new products, ethyl esters of thi process of making cellulose derival- '24. As new roducts, esters of, thiourethamido group is replaced by an a cohol radi- 25. As new products, esters of thiourethanes of the cellulose group in which thi-.

thiourethanes at least one hydrogen atom of-- V the amide group is replaced y. anaryl oup. '29.;As" new'products, alkyl esters of thiourethanes of the cellulose group in which thiou'rethanes at least one hydrogen atom of Jjthe amido group is replaced by a phenyl groupu' 30. As new products, ethyl esters of thi- .ourethanes of the. cellulose ydrogen atom of the-amido group is replaced bya phenyl glroup in which i 31. As new.

'an'esof the ce ulosefigroup'in which thiouroducts, esters of thiourethrethanes at least one hydroxyl-hydrogen atom of the'cellulose component is replaced "by an alcohol radical.

32. As new products, esters of thiourethanes of the cellulose group in which thiourethanesat least one hydroxyl-hydrogen atom of it; cellulose component is replaced an a oup. 33. As nevg roducts, esters of thiourethanes of the cel ulose group in which thiou rethanes at least one hydroxyl-hydrogen atom of the cellulose component is replaced b an ethl ou'.

34. As he? r ducts, esters of thiourethanes of the cellulose group in which .thiourethanes at least one hydrogen atom of the amido group is replaced by an alcohol radical and at least one hydrogyl-hydrogen atom of the cellulose component is replaced by an alcohol radical.

As new products, esters of thiourethanes of the cellulose roup in which thiourethanes at least one ydrogen atom of the amido group is replaced by an aryl group andatle'ast one hydroxyl-hydrogen atom of the cellulose component is' replaced by an alkyl group,

36. As new products, esters of thlourethanes of the'cellulose group in which -th1- ourethanes atleast one hydrogen atom of the amido group is replaced by aphenyl group in character.

39. As new products, cellulose compounds I and at least one hydroxyl hydrogen atom of the cellulose component is replaced by an eth l oup.

3 s newproducts, cellulose compounds .contammg sulphur which dissolve in volatile solvents which are not basic in character.

38. As new products, cellulose compounds containing sulphur and nitrogen which dissolve in volati esolventswhich' are not basic containing sulphur which dissolve in benzolalcohol mixture, meth'yl alcoholsmethylace-.

tate mixture, and alcohol-acetone mixture.

40. As new products, cellulose compounds containingesulphur and nitrogen which dissolve in nzol-alcohol mixture, methyl-alcohol-methylacetate mixture,- and alcohol-= acetone mixture. Y

.of an alkali metal.-

I 41. As new products, artificial materials,

which consist of an ester of a thiourethane of the cellulose group.

42. As new products, artificial materials which contain an ester of a thiourethane oi the cellulose group. 43. As new products, artificial-.materials,

which consist of an ester of a thiourethane of.

the cellulose group in which thiourethane, at

least one hydrogen atom of the amido group is replaced by an alcohol radical.

44. As new products, artificial materialsi which contain an ester of a thiourethane o v the cellulose group in which thiourethane at {least one hydrogen atom of the amido group is replaced by an alcohol radical.

45. As new products, artificial materials,

which consist of an ester of a thiourethane of ester of an inorganlc acid upon a derivative of a cellulose thiourethane obtained by reacting upon a cellulose thiourethane with an alkali.

48. The process of making cellulose derivatives which comprises reactmg with an ester of an inorganic acid upon a derivative of a cellulose thiourethane obtained by reacting upon a cellulose thiourethane with a hydrox-.

ide of an alkali metal. 49. The process of making cellulose derivat v the atives which comprises reactlng with an ester .of an inorganic acid upon a derivative ofan Nrsubstituted thiourethane of cellulose -obtained by reacting upon an N-substituted thlourethane of cellulose with. a hydroxide In testimony whereof I aflii: ihysi ature. LEON LILIENF LD. 

